Molecular layering of phosphorus oxide structures on the surface of gamma alumina

Phosphorus oxide structures were synthesized on the surface of porous gamma alumina, with phosphorus oxychloride and water vapors used as reagents for successive and alternating (up to four times) treatment of a solid-phase matrix by the molecular layering method with in situ monitoring of the process. It was shown that this procedure yields a double-phase system constituted by a core (aluminum oxide) and shell (amorphous phosphorus oxide layer) with a prescribed chemical composition and structure with characteristics dependent on the number of molecular layering cycles. With increasing treatment rate (from 1 to 4) of the solid-phase matrix with halide and water vapors, the concentration of phosphorus in the samples steadily grows. In the process, the specific surface area, pore volume, and pore size in the double-phase system being formed become smaller. The results obtained in the study are of interest for development of catalytic, sorption, and other functional systems of the core–shell type.     

Chemical equilibrium in a heterogeneous fluid phase system: thermodynamic regularities and topology of phase diagrams

Singularities of the systems with simultaneous phase and chemical equilibria were examined. The thermodynamic regularities were revealed and topology of phase diagrams was presented for multicomponent heterogeneous systems including two or several equilibrium liquid phases (solution layering). The thermodynamic conditions for displacement of phase and chemical equilibrium are considered.     

Quantum-chemical approaches to identification of nanostructures synthesized by molecular layering technique

Identification of nanostructures synthesized on silica surface by molecular layering technique was discussed with the example of vanadium oxide systems. Variation of technological factors in synthesis of the nanostructures was analyzed from the standpoint of controlling their chemical composition and local structure, as well as in the context of relationships with the stability and functional characteristics. It was shown that, based on chemical analysis and vibrational spectroscopy data, the element-containing nanostructures can be identified only ambiguously, while a promising alternative can be found in quantum-chemical modeling. The optimal modeling modes and methods were elucidated with the use of the cluster approach. The Gaussian03 calculations showed that the Si-O-V stretching vibration frequency varies with the number of the metal-silica surface bonds. The predictions for nanosystems with different local structures quantitatively agree with the experimental spectral characteristics and are suitable for identification of the objects examined.     

The effect exerted by temperature on the phase formation of titanium oxide layer on silica surface at different stages of molecular layering

The effect exerted by thermal conditions at the different stages of the molecular layering synthesis on the structure and phase composition of a coating being formed was studied for the example of the system silica matrix: titanium dioxide surface layer.     

Possibility of quantum chemical evaluation of the probability of various chemical transformations in syntheses of phosphorus-, titanium-, silicon-, and vanadium-containing structures on the silica surface

Application of minimum quantum-chemical models for predicting chemical transformations in syntheses of phosphorus-, titanium-, silicon-, and vanadium-containing structures on the silica gel surface by molecular layering is considered. Possible pathways for transformation of the groups synthesized under the action of water vapor and hydrogen chloride are analyzed in terms of the models constructed.     

Perspectives of application of the molecular layer deposition technique for controlling operational properties of materials for shipbuilding

The results of investigations of surface modification of glass hollow microspheres are summarized. The regularities of the chemical molecular layering nanotechnology and its application for production of fillers and composite materials of low density with improved operational properties are discussed. Influence of chemical modification on thermal stability and combustibility of various polymer composites is investigated.     

Quantum-chemical analysis and experimental study of the process of the silica surface interaction with the CrO<Subscript>2</Subscript>Cl<Subscript>2</Subscript> and VOCl<Subscript>3</Subscript> vapor mixture

We accomplished a synthesis of the two-component vanadium-chromium containing monolayer on the silica surface by treating the latter with a mixture of CrO₂Cl₂ and VOCl₃ vapors. Analysis of the chemical reactions on the substrate surface is carried out using quantum-chemical modeling. The calculated VOCl₃ reactivity is higher than that of CrO₂Cl₂, which requires the use of an excess of the chromium oxychloride in the reaction mixture to provide a control over the coating composition in a wide range of concentrations. The quantitative forecast of the reaction product composition indicates a significant role of the synthesis temperature and structural strain at the formation of the monolayer. We carried out an experimental synthesis of the two-component coating by the method of molecular layering (ML) under the conditions derived from quantum-chemical predictions, at a concentration ratio of chromium and vanadium in the range from 0.5 to 2.6, and showed the ability of control over the product composition. Based on a comparison of experimental and calculated data the structural strains and the quantitative ratio of the surface centers of different local structure were estimated. The results obtained using infrared Fourier spectroscopy confirm the agreement between the experimental data and the quantum-chemical predictions.     

Density functional theory model of adsorption on amorphous and microporous silica materials

We present a novel quenched solid density functional theory (QSDFT) model of adsorption on heterogeneous surfaces and porous solids, which accounts for the effects of surface roughness and microporosity. Within QSDFT, solid atoms are considered as quenched component(s) of the solid-fluid system with given density distribution(s). Solid-fluid intermolecular interactions are split into hard-sphere repulsive and mean-field attractive parts. The former are treated with the multicomponent fundamental measure density functional. Capabilities of QSDFT are demonstrated by drawing on the example of adsorption on amorphous silica materials. We show that, using established intermolecular potentials and a realistic model for silica surfaces, QSDFT quantitatively describes adsorption/desorption isotherms of Ar and Kr on reference MCM-41, SBA-15, and LiChrosphere materials in a wide range of relative pressures. QSDFT offers a systematic approach to the practical problems of characterization of microporous, mesoporous, and amorphous silica materials, including an assessment of microporosity, surface roughness, and adsorption deformation. Predictions for the pore diameter and the extent of pore surface roughness in MCM-41 and SBA-15 materials are in very good agreement with recent X-ray diffraction studies.     

N，N′-双(3-羧基水杨醛叉缩胺乙基)草酰胺均双核铜(II)的密度泛函研究

草酰胺及其衍生物过渡金属原子配合物是近年来在实验和理论上[1￣5]研究都十分活跃的领域,其原因是这些配合物具有良好的磁性质,对磁功能分子设计和磁性材料合成有着十分重要的意义。我们课题组合成了一种以N,N′-双(3-羧基水杨醛叉缩胺乙基)草酰胺为配体的Cu!-Cu!均双核配合物,由于该配合物的溶解性较差,难以培养出理想的单晶,因此一直未曾进行晶体结构解析。所以,该配合物分子的电子结构特征和几何构型,电子结构与配合物分子的稳定性及分子的磁性之间的构效关系等目前尚不清楚。因此,就该类磁功能配合物分子的上述问题进行理论研究,无疑…     

Calculation of the Stoichiometric Composition of Nanostructures Synthesized by Molecular Layer Deposition on the Surface of Solid Matrices

Calculational formulas for determining from the results of chemical and thermogravimetric analyses the true relative contents of components in products formed in molecular layer deposition of nanostructures on the surface of solid matrices are suggested. The approaches considered are illustrated by the example of evaluation of the chemical composition of titanium oxide (nitrogen) and silicon-nitrogen nano-layers synthesized by molecular layer deposition on the silica surface.__________Translated from Zhurnal Prikladnoi Khimii, Vol. 78, No. 3, 2005, pp. 373–379.Original Russian Text Copyright © 2005 by Sosnov, Malkov, Malygin.     

亚胺类共价有机骨架材料在样品前处理中的应用

亚胺类共价有机骨架(I-COFs)是有机单体根据席夫碱(Schiff-base)反应原理缩合形成的一类新型多孔晶体有机材料.I-COFs具有骨架密度低、比表面积大、孔隙率高、单体种类丰富、孔径尺寸可控、结构可功能化、合成方法多样和物化稳定性好等优点.近年来,I-COFs已成为材料科学领域的研究前沿,并广泛用于气体吸附、...     

Synthesis of radialene-shaped pyrroles by multiple-anion-capture reactions of 1,3-dianions

A new multicomponent reaction (multiple-anion-capture reaction) of 1,3-dianions with nitriles and oxalic acid-bis(imidoyl)chlorides is reported. This process allows for an efficient and regioselective synthesis of a variety of radialene-shaped pyrroles which constitute structurally new and interesting heterocyclic systems. The cyclization products can be considered as aza-analogues of the pharmacologically relevant substance class of 3-acetyltetramic acids. A rationalization of the experimental results is given based on quantum chemical computations.     

Understanding and Manipulating Inorganic Materials with Scanning Probe Microscopes

Scanning probe microscopies, such as scanning tunneling microscopy and atomic force microscopy, are uniquely powerful tools for probing the microscopic properties of surfaces. If these microscopies are used to study low-dimensional materials, from two-dimensional solids such as graphite to zero-dimensional nanostructures, it is possible to elucidate atomic-scale structural and electronic properties characteristic of the bulk of a material and not simply the surface. By combining such measurements with chemical synthesis or direct manipulation it is further possible to elucidate relationships between composition, structure, and physical properties, thus promoting an understanding of the chemical basis of material properties. This article illustrates that the combination of scanning probe microscopies and chemical synthesis has advanced our understanding of charge density waves, high-temperature superconductivity, and nanofabrication in low-dimensional materials. This new approach to studying materials has directly contributed to our knowledge of how metal dopants interact with charge density waves and elucidated the local crystal chemistry of complex copper oxides, microscopic details of the superconducting states in materials with a high superconducting transition I_c, and new approaches to the fabrication of multi-component nanostructures. Coupling scanning probe microscopy measurement and manipulation with chemical synthesis should provide an approach to understanding material properties and creating complex nanostructures in general.     

Surface-Confined Self-Assembly of Asymmetric Tetratopic Molecular Building Blocks

Surface-confined self-assembly of functional molecular building blocks has recently been widely used to create low-dimensional, also covalent, superstructures with tailorable geometry and physicochemical properties. In this contribution, using the lattice Monte Carlo simulation method, we demonstrate how the structure-property relation can be established for the 2D self-assembly of a model tetrapod molecule with reduced symmetry. To that end, a rigid functional unit comprising a few interconnected segments arranged in different tetrapod shapes was used and its self-assembly on a triangular lattice representing a (111) crystal surface was simulated. The results of our calculations show strong dependence of the structure formation on the molecular symmetry, in particular on the (pro)chiral nature of the building block. The simulations predicted the formation of unusual ordered racemic networks with unique aperiodic spatial distribution of the surface enantiomers. Molecular symmetry was also found to have significant influence on the enantiopure self-assembly which resulted in the Kagome and brickwall networks and other less ordered extended superstructures with parallelogram pores. The theoretical findings of this contribution can be relevant to designing and on-surface synthesis of molecular superstructures with predefined geometries and functions. In particular, the predicted molecular architectures can stimulate experimental efforts to fabricate and explore new nanostructures, for example graphitic, having the composition and geometry proposed in our study.     

Chemistry of aqueous silica nanoparticle surfaces and the mechanism of selective peptide adsorption

Control over selective recognition of biomolecules on inorganic nanoparticles is a major challenge for the synthesis of new catalysts, functional carriers for therapeutics, and assembly of renewable biobased materials. We found low sequence similarity among sequences of peptides strongly attracted to amorphous silica nanoparticles of various size (15-450 nm) using combinatorial phage display methods. Characterization of the surface by acid base titrations and zeta potential measurements revealed that the acidity of the silica particles increased with larger particle size, corresponding to between 5% and 20% ionization of silanol groups at pH 7. The wide range of surface ionization results in the attraction of increasingly basic peptides to increasingly acidic nanoparticles, along with major changes in the aqueous interfacial layer as seen in molecular dynamics simulation. We identified the mechanism of peptide adsorption using binding assays, zeta potential measurements, IR spectra, and molecular simulations of the purified peptides (without phage) in contact with uniformly sized silica particles. Positively charged peptides are strongly attracted to anionic silica surfaces by ion pairing of protonated N-termini, Lys side chains, and Arg side chains with negatively charged siloxide groups. Further, attraction of the peptides to the surface involves hydrogen bonds between polar groups in the peptide with silanol and siloxide groups on the silica surface, as well as ion-dipole, dipole-dipole, and van-der-Waals interactions. Electrostatic attraction between peptides and particle surfaces is supported by neutralization of zeta potentials, an inverse correlation between the required peptide concentration for measurable adsorption and the peptide pI, and proximity of cationic groups to the surface in the computation. The importance of hydrogen bonds and polar interactions is supported by adsorption of noncationic peptides containing Ser, His, and Asp residues, including the formation of multilayers. We also demonstrate tuning of interfacial interactions using mutant peptides with an excellent correlation between adsorption measurements, zeta potentials, computed adsorption energies, and the proposed binding mechanism. Follow-on questions about the relation between peptide adsorption on silica nanoparticles and mineralization of silica from peptide-stabilized precursors are raised.     

Density functional approach to adsorption of simple fluids on surfaces modified with a brush-like chain structure

A density functional theory to describe adsorption of a simple fluid from a gas phase on a surface modified with pre-adsorbed chains is proposed. The chains are bonded to the surface by one of their ends, so they can form a brush-like structure. Two models are investigated. According to the first model all but the terminating segment of a chain can change the configuration during the adsorption of fluid species. The second model assumes that the chains remain "frozen", and the system is considered as a nonuniform quenched-annealed mixture. We apply simple form of interactions to study adsorption phenomena, microscopic structure, and layering transitions. Our principal findings show that new layering phase transitions can occur because of a chemical modification of the substrate under certain conditions, in comparison with nonmodified surfaces. However, opposite trends, that is, smoothing the adsorption isotherms, can also be observed, depending on the surface density of the grafted chains.     

Harnessing the Capabilities of Spray Granulation in the Food Industry for the Production of Functional Foods

The article is the literature review of a current state of production technologies of powdery foodstuff, concentrates and multicomponent mixes. The need of the food industry for qualitative methods of processing of raw materials of different physical and chemical structure is noted. The authors give the reasons about need and possibility of a choice of granulation as a method of data processing of products. Physical and chemical features of granulation methods of disperse environments of various aggregate states based on the studied regularities and works of other authors are considered. The authors made the assumption of the application prospects of the method of liquid dispersion on the surface of particles in a suspended state for a granulation of foodstuff and they offered the alternative option. The possibility to use whey as binding element is considered. At the end of article authors draw the conclusion about the prospects of use of a method of dispersion of liquid on the surface of particles in a suspended state for a granulation of foodstuff.     

Orthogonally reactive SAMs as a general platform for bifunctional silica surfaces

We report the synthesis and self-assembly of azide and amine trimethoxysilanes that result in mixed monolayers on silica. The amine and azide functional groups can be independently reacted with acid chlorides and terminal alkynes, respectively. Consequently, these orthogonally reactive monolayers represent a general starting point for making bifunctional surfaces. Using X-ray photoelectron spectroscopy, we determined the azide/amine surface ratio as well as the reactivity of the azide and amine functional groups in the mixed self-assembled monolayer (SAM). Significantly, the surface azide/amine ratio was much lower than the azide/amine ratio in the self-assembly mixture. After determining the self-assembly mixture composition that would afford 1:1 azide-amine mixed monolayers, we demonstrated their subsequent functionalization. The resulting bifunctional surface has a similar functional group ratio to the azide/amine precursor SAM demonstrating the generality of this approach.     

Lipid A-Mediated Bacterial–Host Chemical Ecology: Synthetic Research of Bacterial Lipid As and Their Development as Adjuvants

Gram-negative bacterial cell surface component lipopolysaccharide (LPS) and its active principle, lipid A, exhibit immunostimulatory effects and have the potential to act as adjuvants. However, canonical LPS acts as an endotoxin by hyperstimulating the immune response. Therefore, LPS and lipid A must be structurally modified to minimize their toxic effects while maintaining their adjuvant effect for application as vaccine adjuvants. In the field of chemical ecology research, various biological phenomena occurring among organisms are considered molecular interactions. Recently, the hypothesis has been proposed that LPS and lipid A mediate bacterial–host chemical ecology to regulate various host biological phenomena, mainly immunity. Parasitic and symbiotic bacteria inhabiting the host are predicted to possess low-toxicity immunomodulators due to the chemical structural changes of their LPS caused by co-evolution with the host. Studies on the chemical synthesis and functional evaluation of their lipid As have been developed to test this hypothesis and to apply them to low-toxicity and safe adjuvants.     

Stepwise Adsorption of Alkoxy-Pyrene Derivatives onto a Lamellar,Non-Porous Naphthalenediimide-Template on HOPG

The development of new strategies for the preparation of multicomponent supramolecular assemblies is a major challenge on the road to complex functional molecular systems. Here we present the use of a non-porous self-assembled monolayer from uC₃₃-NDI-uC₃₃ , a naphthalenediimide symmetrically functionalized with unsaturated 33 carbon-atom-chains, to prepare bicomponent supramolecular surface systems with a series of alkoxy-pyrene ( PyrOR ) derivatives at the liquid/HOPG interface. While previous attempts at directly depositing many of these PyrOR units at the liquid/HOPG interface failed, the multicomponent approach through the uC₃₃-NDI-uC₃₃ template enabled control over molecular interactions and facilitated adsorption. The PyrOR deposition restructured the initial uC₃₃-NDI-uC₃₃ monolayer, causing an expansion in two dimensions to accommodate the guests. As far as we know, this represents the first example of a non-porous or non-metal complex-bearing monolayer that allows the stepwise formation of multicomponent supramolecular architectures on surfaces.